<p>This study focuses on the design and application of calcium alginate/gum arabic/eggshell powder composite microbeads (CA/GA/ES10) for the removal of methylene blue dye from aqueous solutions through the adsorption method. The characterization of adsorbents was conducted utilizing ATR-FTIR, SEM, XRD, TGA, and pH<sub>pzc</sub>. The pH<sub>pzc</sub> value of CA/GA/ES10 composite microbeads was determined as 5.56. From optimization studies, the contact time, adsorbent dosage, and pH values were determined as 60&#xa0;min, 0.1&#xa0;g/50&#xa0;mL, and ≅ 7, respectively. The adsorption raw data have been utilized in the non-linear Langmuir, Freundlich, Temkin, and Sips models. The maximum adsorption capacity of CA/GA/ES10 composite microbeads, as per the Sips, was determined to be 33.30&#xa0;mg/g at 298&#xa0;K. The high correlation coefficients (<InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="13233_2025_408_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="16" /> </InlineMediaObject> <EquationSource Format="TEX">\(r^{2}\)</EquationSource> <EquationSource Format="MATHML"><math> <msup> <mi>r</mi> <mn>2</mn> </msup> </math></EquationSource> </InlineEquation> = 0.9976) and low error functions (<InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="13233_2025_408_Article_IEq2.gif" Format="GIF" Height="19" Rendition="HTML" Resolution="72" Type="Linedraw" Width="19" /> </InlineMediaObject> <EquationSource Format="TEX">\(\chi^{2}\)</EquationSource> <EquationSource Format="MATHML"><math> <msup> <mi>χ</mi> <mn>2</mn> </msup> </math></EquationSource> </InlineEquation> = 0.03) indicate that the non-linear Langmuir is the most appropriate isotherm for the adsorption process. From the Langmuir model, the maximum adsorption capacity was determined as 29.71&#xa0;mg/g at 298&#xa0;K. The adsorption process adheres to a non-linear pseudo-second-order (<InlineEquation ID="IEq3"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="13233_2025_408_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="16" /> </InlineMediaObject> <EquationSource Format="TEX">\(r^{2}\)</EquationSource> <EquationSource Format="MATHML"><math> <msup> <mi>r</mi> <mn>2</mn> </msup> </math></EquationSource> </InlineEquation> = 0.9999) and Elovich (<InlineEquation ID="IEq4"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="13233_2025_408_Article_IEq1.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="16" /> </InlineMediaObject> <EquationSource Format="TEX">\(r^{2}\)</EquationSource> <EquationSource Format="MATHML"><math> <msup> <mi>r</mi> <mn>2</mn> </msup> </math></EquationSource> </InlineEquation> = 0.9999) models. According to thermodynamic results, the adsorption process occurs exothermic (<InlineEquation ID="IEq5"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="13233_2025_408_Article_IEq5.gif" Format="GIF" Height="21" Rendition="HTML" Resolution="72" Type="Linedraw" Width="156" /> </InlineMediaObject> <EquationSource Format="TEX">\(\Delta H^{^\circ } = - 3.77\;{\text{kJ/mol}}\)</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mi mathvariant="normal">Δ</mi> <mmultiscripts> <mi>H</mi> <mrow /> <mmultiscripts> <mrow /> <mrow /> <mo>∘</mo> </mmultiscripts> </mmultiscripts> <mo>=</mo> <mo>-</mo> <mn>3.77</mn> <mspace width="0.277778em" /> <mtext>kJ/mol</mtext> </mrow> </math></EquationSource> </InlineEquation>) and spontaneous (<InlineEquation ID="IEq6"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="13233_2025_408_Article_IEq6.gif" Format="GIF" Height="21" Rendition="HTML" Resolution="72" Type="Linedraw" Width="227" /> </InlineMediaObject> <EquationSource Format="TEX">\(\Delta G^{^\circ } = - 25.83\;{\text{kJ/mol}}\;{\text{at}}\;298\;{\text{K}}\)</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <mi mathvariant="normal">Δ</mi> <mmultiscripts> <mi>G</mi> <mrow /> <mmultiscripts> <mrow /> <mrow /> <mo>∘</mo> </mmultiscripts> </mmultiscripts> <mo>=</mo> <mo>-</mo> <mn>25.83</mn> <mspace width="0.277778em" /> <mtext>kJ/mol</mtext> <mspace width="0.277778em" /> <mtext>at</mtext> <mspace width="0.277778em" /> <mn>298</mn> <mspace width="0.277778em" /> <mtext>K</mtext> </mrow> </math></EquationSource> </InlineEquation>) in nature. The impact of varying salt concentrations on the adsorption process was assessed. According to the salt effect, the removal percentage decreased from 81.12 to 65.15% with the addition of NaCl, and from 81.12 to 58.78% with the addition of CaCl<sub>2</sub>. The reusability tests show that the composite microbeads created can be used repeatedly for up to 7 cycles. After the 7th cycle, the removal of MB dye decreased from 81.11 to 53.45%. All results showed that the prepared ternary composite microbeads are effective adsorbents for the removal of cationic dye from aqueous solutions.</p> Graphical abstract <p></p>

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Fabrication of calcium alginate/gum arabic/egg shell composite microbeads for adsorptive removal of methylene blue dye from aqueous solutions

  • Melike Nisa Sandikci,
  • Birol Isik

摘要

This study focuses on the design and application of calcium alginate/gum arabic/eggshell powder composite microbeads (CA/GA/ES10) for the removal of methylene blue dye from aqueous solutions through the adsorption method. The characterization of adsorbents was conducted utilizing ATR-FTIR, SEM, XRD, TGA, and pHpzc. The pHpzc value of CA/GA/ES10 composite microbeads was determined as 5.56. From optimization studies, the contact time, adsorbent dosage, and pH values were determined as 60 min, 0.1 g/50 mL, and ≅ 7, respectively. The adsorption raw data have been utilized in the non-linear Langmuir, Freundlich, Temkin, and Sips models. The maximum adsorption capacity of CA/GA/ES10 composite microbeads, as per the Sips, was determined to be 33.30 mg/g at 298 K. The high correlation coefficients ( \(r^{2}\) r 2  = 0.9976) and low error functions ( \(\chi^{2}\) χ 2  = 0.03) indicate that the non-linear Langmuir is the most appropriate isotherm for the adsorption process. From the Langmuir model, the maximum adsorption capacity was determined as 29.71 mg/g at 298 K. The adsorption process adheres to a non-linear pseudo-second-order ( \(r^{2}\) r 2  = 0.9999) and Elovich ( \(r^{2}\) r 2  = 0.9999) models. According to thermodynamic results, the adsorption process occurs exothermic ( \(\Delta H^{^\circ } = - 3.77\;{\text{kJ/mol}}\) Δ H = - 3.77 kJ/mol ) and spontaneous ( \(\Delta G^{^\circ } = - 25.83\;{\text{kJ/mol}}\;{\text{at}}\;298\;{\text{K}}\) Δ G = - 25.83 kJ/mol at 298 K ) in nature. The impact of varying salt concentrations on the adsorption process was assessed. According to the salt effect, the removal percentage decreased from 81.12 to 65.15% with the addition of NaCl, and from 81.12 to 58.78% with the addition of CaCl2. The reusability tests show that the composite microbeads created can be used repeatedly for up to 7 cycles. After the 7th cycle, the removal of MB dye decreased from 81.11 to 53.45%. All results showed that the prepared ternary composite microbeads are effective adsorbents for the removal of cationic dye from aqueous solutions.

Graphical abstract